Acylamines of the anthraquinone series and a process for their manufacture



Patented Oct. 3, 1944 UNITED STATES ATENT OFFICE AoYLAmNEs MANUFACTURE OF THE ANTHRAQUINONE SERIES AND A PROCESS FOR THEIR Albin Peter, Basel, Switzerland, assignor to Sandoz A. G., Fribourg, Switzerland, a Swiss 16 Claims.

The present invention relates to new acylamines of the anthraquinone series, which are valuable vat dyestuffs dyeing natural and artificial cellulosic fibres in red to violet shades and to a process for the manufacture of the new acylamines.

It has been found that new acylamines of the anthraquinone series can be obtained by condensing an anthrapyridone compound of the general formula zoy1-, C-acetyl-, C-cyano-anthrapyridone and the like. They can be obtained in known manner, for example by condensation of halogenanthrapyridones with amino benzoic acids, by

condensation of aminoanthrapyridones with halogen benzoic acids, by condensation of ,1- amino 4 (carboxyphenyl) amino anthraquinones with malonic esters, aceto-acetic ester, cyano-acetic ester, benzoyl-acetic ester thus forming the corresponding anthrapyridones. For the preparation of the new acylamines the following carboxyl derivatives may, for instance, be used: N methyl 4 carboxyphenylamino- 1(N) Q-anthrapyridones, C-carbomethoxyand C-carbethoxy- 4 -carboxyphenyl amino 1 (N) 9- anthrapyridones, C-acety1-, C-benzoyl-, C-cyano- 4-carboxyphenylamino 1(N) 9 anthrapyridones and C-carbomethoxyand C-carbethoxy-Z- methyl-4-carboxyphenyl-amino- 1(N) 9 anthrapyridones and the like.

On the other hand, the following vattable amino-anthraquinones containing at least one primary amino group are suitable according to the present invention. Amino-anthraquinones, such as 1- and Z-aminoanthraquinone, l-amino- 3-bromoanthraquinone, 1-amino-5-, -6- -7- and V -8-chloroanthraquinone, 1-amino-6 7,-dichloroanthraquinone, l-amino-4-methoxyanthraquinone, 124-, 1:5-, 1:8- and 2:6-diaminoanthraquinone, 1-amino-4-, -5- and -8-benzoylaminoanthraquinones, 1-amino-4-phenylaminoanthraquinone, 1-amino-4-(2'-chlorophenyl) -(3'- chlorophenyl) (4-chlorophenyl) aminoanthraquinone, l-aminol-(4'-methy1phenyl)-, -(4'- methoxyphenyl) -aminoanthraquinone, l-amino- 4-phenylamino-6- or -7-chloroanthraquinone and the derivatives substituted in the phenyl nucleus by halogen, alkyl or alkoxy; moreover, aminoanthrapyridones, such as 4-amino-N- methyl-1 (N) Q-anthrapyridone, 4-amino-N-methyl-C-acetyland -C-carbethoxyanthrapyridone, 4-amino-2-methyl-C earbethoxy-, C carbomethoXy-, '-C-benzoyl-, -C-acetyl-, -C-cyanoanthrapyridone, 5-amino-C-carbethoxy-1(N) 9-anthrapyridone, come into question, but also aminoanthrapyrimidines, such as 4-amino-1: Q-anthrapyrimidine, 5-amino-1:Q-anthrapyrimidine and finally aminoanthraquinone acridones, such as 4-aminoanthraquinone-2 1- (N) -benzacridone.

The condensation to the new acylamines takes place by heating the carboxyl compounds in a solvent, such as chlorobenzene, o-dichlo'robenzene, nitrobenzene or the like, with phorphorus trichloride, phosphorus pentachloride, thionyl chloride and so on, whereby they are converted into the corresponding acid chloride and, if desired, after separation of the acid chloride and again taking it up in fresh solvent, by further heating the same with the amino compound with or without binding the liberated hydrochloric acid by means of basic substances, such as pyridine, di-methylaniline, alkali-acetate and the like.

The condensation can, however, also be carried out by heating the mixture of the carboxyl compound with the amino compound in a solvent, such as chlorobenzene, o-dichloro-benzene, nitrobenzene and so on, in the presence or absence of an acid binding agent,,such as pyridine, dimethylaniline, alkali-acetate and the like, and with the addition of a condensing agent like phosphorus trichloride, phosphorus pentachloride, thionyl chloride and so on. Thionyl chloride is preferred on account of simplicity in use.

The temperatures required for the condensation vary within wide limits for example from 80 C. to 200 C. The heating is continued until test samples in alcohol show no further diminution of the alcohol-soluble starting materials. When the condensation has completed, the new acylamines are filtered off directly or after dilution with alcohol and purified, if necessary, by boiling with alcohol, glacial acetic acid, o-dichlorobenzene, nitrobenzene, aniline or with a dilute sodium carbonate solution to which sodium hypochlorite may be added, if desired.

The new acylamines may be used as vat dyes and as starting materials for other dyestuffs.

The following examples, without being limitative, illustrate the present invention. The parts are by weight.

EXAMPLE 1 7.9 parts of N-methyl-4-(3-carboxy)-pheny1- amino-1(N)Q-anthrapyridone are heated to 140 C. with 6.9 parts of l-aminol-benzoylaminoanthraquinone and 200 parts of 1:2-dichlorobenzene and the mass is completely freed from water by conducting over it a current of dry air during 2 hours. Thereupon 3 parts of thionyl chloride are added under stirring and the temperature is maintained at 150 C. during 6 hours, then at 130 C. for further 6 hours. After cooling down to 100 C. 100 parts of alcohol are added; the dyestufi is filtered by suction, washed with alcohol and water and finally dried.

dyes natural and regenerated cellulose from a dark-red vat in a blue-red shade.

EXAMPLE 2 7.9 parts of N-methyl-4-(4'-carboxy) -pheny1- amino-1(N)Q-anthrapyridone are heated in 200 parts of 1:2-dichlorobenzene to 140 C. and the mixture is freed from water in the manner indicated in Example 1.- Then 2.3 parts of thionyl chloride are added at 100 C. to this mixture and the mass stirred at this temperature during 6 hours. 4.5 parts of 2-aminoanthraquinone are now introduced thereintoand the whole stirred during 20 hours at 130 C. After having reduced ,the temperature to 90. C. 100 parts of alcohol are added and the dyestuif separated by filtration. It is washed and dried in the usual manner.

The new dyestufi possesses the formula ll C I ON It dyes cotton from a red-orange vat in a bluish: red shade.

EXAMPLE 3 To a mixture of 8.7 parts of N-methyl-4-(4'- carboxy) phenylamino -1 (N) 9 anthrapyridone with 200 parts of trichlorobenzene and 2.6 parts 5 of thionyl chloride, which has been stirred for lated in the usual manner.

5 hours at 100 C., 2.5 parts of pyridine and 2.4 parts of 1:4-diaminoanthraquinone are added and the temperature maintained at 180 C. during 9 hours. The dyestufi thus produced is iso- It dyes cotton from a dark-red vat in blue-red shades and possesses the formula phenylamino-1(N)Q-anthrapyridone are stirred for 10 hours with 20 parts of thionyl chloride and parts of chlorobenzene at 75 C. After cooling down the obtained acid chloride is separated and dried in vacuo at C.

9.9 parts of this product are introduced at 100 C. into a mixture of 6.9 parts of l-aminolbenzoylaminoanthraquinone, 200 parts ofnitrobenzene and 2.5 parts of pyridine and the whole is stirred for 18 hours at 100 C. After dilution with alcohol the dyestufi is separated, washed 0 and dried. It forms with hydrosulphite a darkred vat, dyeing cotton in a blue-red shade.

It possesses the formula:

if QW EXAMPLE. 5

phenylamino-l (N) Q-anthrapyridone is diluted with 100 parts of alcohol.

added thereto u'nder stirring; stirring is continued brown vat.

It possesses the formula The separated dyestufi having the formula is filtered, washed and dried. It dyes cotton from a dark-red vat in blue-red shades.

O CzHs for a further hour at 150 C. Then 8.9 parts of 5-amino-1:1-dianthrimide are added and stirred for further 6 hours at 180 C. The new dye is obtained by dilution with alcohol and filtration. It dyes cellulose threads bordeaux red from a red- A number of dyes obtained by the process herein described are summarised in the following table.

Talble Acylating medium Primary amine Color of the vat fi'g? on N-m thyl-io-earboxyphenylamino-l(N)9-anthrapyridone l-amino-fiehloroanthraquinone Red-brown Violet.

D 1:4-diaminoanthraquinone Red-violet.

1 amino 4 (4 methoxy phenyl) amino- Violet.

anthraquinone. 1:5-diaminoanthraquinone Red. 1-amino-5-benzoylaminoanthraqrfino Bordeaux-red. Do 4-amino-N-methylanthrapyridone 1(N)9-C-carbethoxy-2-methyl-4-o-carboxyphenylamjno- 1:5-diammoanthraqu1none Red. anthrapyridone. 1(N)Q-methy1-4-m-earboxyphenylaminoanthrapyridone lil-dlfiIIllDOfiHthlfifllllIlOnQ Pink, (N)9-C- b thoxyi-m-ca.rboxyphenylaminoanthra- 2-anm1o-anthraqu1none Dark ora ge Blue-red.

idone. l o 4-amino-N-methylanthrapyridon d Red bmwn 9-() b 1;g y-4-(3'-carboxy-4'-chlorophenyl)-amil-aminoanthraquinone Red-brown Brown-violet.

noanthra i one. 1.(N. thg 9-4-p-oarboxyphenylaminoanthrapyridone 1-1finino- 4- (4-chloro-pheny1)-aminoan- Dark red Red-violet.

raquinone. 1(N-methyl)9-4-p-carboxyphenyl-aminoanthrapyridone 1i5-diamino anthraquinone Blamed o 4-am no-N-methylanthrapyndon 9.0. b th 4- -carboxyphenylaminoanthrapyril-ammoanthraquinone Dark-red Blue-red.

p 2-aminoanthraquinone Dark orange Bordeauxnd.

lA-diaminoanthraquinone D Ruby red. l-amino-4-(4-ch1oro-phenyl)-aminoa.nthra- Red-violet.

qmnone. V 1:5-diamino-anthraquinone Blue-red. 2:6-diamino-ahthraquinone. Bordeaux-red. D0 Diaminoanthrarufine Violet. 1(N)9-C-carbethoxy- -p-carboxyphenylaminoanthrapy- 4-am1no-l- (N -methy1) 9-O-carbethoxy Bl -r d,

ridmm anthrapyridone. 1(N)9-C-acetyl-4-p-carboxyphenyl-aminoanthmpyridone i-am no-N-methylanthrapyridone Dark ted-brown... Do. 1 (N) 9-methyl-4-m-carboxy-phenyl-aminoanthrapyridone l-amino-4-benzoylam no-anthraquinone Dark red Do.

Do 1am no-5-be11zoylammo-anthraquinone Yellow-red. 1 (N) 9-methy1-4-m-carboxy-phenyl-amino-anthrapyri- 1-ammo-4-1nethoxyanthra-quinone Red.

done. 1 (N) 9.0. -b thoxy-4-p-ca1-boxypheny1-amm0anthra 1ammo-4-methoxy-anthra-qumone do Blue-red.

n f l-amino-4-benzoy1-aminoanthra-qu1n0ne Dark-red Do.

Do li-gminoanthra-quinonefil-(Nj-benzacri- Red-violet Dark red-violet.

one. N- th 1-4-(3' carboxy)-phenyl-am.inoanthra-pyri- 4:4-diamino-1:l-dianthrimide Brown Corinth.

d ne. N-r ethyl-i-(4-carboxy)-phenyl-aminoanthra-pyridone 5-am1 no1:2-d anthr m de.. Red-brown Bordeaux-red. 4'. x heny1smino-anthrapyridone 5-am1n0-1:2-d1anthr1m1deo Do.

EXAMPLE 6 This application is a division of my application What I claim is:

Ser. No. 427,076, filed January 16, 1942.

1. A process for the manufacture of new acylamines of the anthraquinone series, comprising the step of condensing an anthrapyridone pound of the general formula comwherein R stands for a member of the group consisting of hydrogen and alkyl, R1 stands for a member of the group consisting of hydroxy and halogen and X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy, with a vattable anthraquinone compound containing at least one primary amino group.

2. A process for the manufacture of new acylamines of the anthraquinone series, comprising the step of condensing an anthrapyridone compound of the general formula wherein R stands for a member of the group consisting of hydrogen and alkyl and X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy, with a vattable anthraquinone compound containing at least one primary amino group in presence of an organic solvent.

4. A process for the manufacture of new acylamines of the anthraquinone series, comprising the step of condensing an anthrapyridone compound of the general formula wherein R stands for a member of the group consisting of hydrogen and alkyl and X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy, with a vattable anthraquinone compound containing at least one primary amino group in presence of an organic solvent. I

5. A process for the manufacture of new acylamines of the anthraquinone series, comprising the step of condensing an anthrapyridone compound of the general formula wherein X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy, with a vattable anthraquinone compound containing at least one primary amino group in presence of an organic solvent.

6. A process forthe manufacture of new acylamines of the anthraquinone series, comprising the step of condensing the anthrapyridone compound of the formula with a vattable anthraquinone compound containing at least one primary amino group in presence of an organic solvent.

'7. A process for the manufacture of a new acylamine of the anthrapyridone series, comprising the step of condensing the anthrapyridone compound of the formula H o NHOC 0 G1 with 1-amino-4-benzoylaminoanthraquinone in presence of an organic solvent. 20

8. A process for the manufacture of a new acylamine of the anthrapyridone series, comprising the step of condensing the anthrapyridone compound of the formula with 1:4-diaminoanthraquinone in presence of an organic solvent.

9. A process for the manufacture of a new acylamine of the anthrapyridone series, comprising the step of condensing the anthrapyridone compound of the formula H NH 0 II OOCl wherein X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy, R stands for a member of the group consisting of hydrogen and alkyl and A stands for avattable anthraquinone radical, which acylamines are vat dyestuffs possessing afiinity for fibres of cellulosic nature and dyeing the same in red to violet shades.

11. The new acylamines of the anthraquinone series possessing the general formula wherein X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy, R stand for a member of the group consisting of hydrogen and alkyl and A stands for a vattable anthraquinone radical, which acylamines are vat dyestuffs possessing aifinity for fibres of cellulosic nature and dyeing the same red to violet shades.

12. The new acylamines of the anthraquinone series possessing the general formula wherein X stands for a member of the group consisting of hydrogen, acyl, cyano and carbalkoxy and A stands for a vattable anthraquinone radical, which acylamines are vat dyestufis possessing affinity for fibres of cellulosic nature and dyeing the same red to violet shades.

13. The new acylamines of the anthraquinone series possessing the general formula wherein radical, which compounds are vat dyestuffs A stands for a vattable anthraquinone possessing affinity for fibres ofcellulosic nature 15. The new anthrapyridone derivative of the and dyeing the same red to violet shades. formula 14. The new acylamine of the formula 0 I i Q t E5010 0 NH C2HaOC--C \N'H Y H o NEE-GO O-NH o i NHOCO-NH o f NHOCO-NH 0 I] H 0 0 0 NH O00 NH 0 5 a o 0 i II II 0 0 being a. valuable vat dyestufi' and dyeing cotton a blue-red shade. being avaluable vat dyestuff and dyeing cotton 16. The new anthrapyridone derivative of the a blue-red shade. formula being a valuable vat dyestufi and dyeing cotton a bluish-red shade.

ALBIN PETER. 

